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Symmetry and Group

Theory

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Symmetry Operations
A symmetry operation transforms an object into an
indistinguishable form. The center of mass does not move. The main types
of symmetry operation are:

 E - identity
 Cn - rotation by 2/n, where n is an integer
 v - mirror plane containing the principal axis
 d - mirror plane containing the principal axis and the bisector between C2
axes perpendicular to the principal axis. This is a property of higher-
symmetry figures (e.g., benzene, methane).
 h - mirror plane perpendicular to the principal axis
 i - inversion in the center of mass (i.e., x,y,z -x,-y,-z)
 Sn - rotation by 2/n followed reflection in a plane perpendicular to the
symmetry axis. Sometimes called an improper rotation. Also, the reflection
plane does not have to be a symmetry plane of the figure. (Note that S2
inversion).

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Examples
For every figure, there is a unique set of symmetry operations, which
form a group. We assign each geometrical figure to a point group.
 Tetrahedron CH4 , CCl4
Point group Td - symmetry operations are E, 8C3, 3C2, 6S4 and 6v
 Water molecule, cis-1,3-butadiene
Point group C2v - symmetry operations are E, C2, v (angle bisector), v (plane
of molecule)
 Trans-1,3-butadiene
Point group C2h - symmetry operations are E, C2, i (or S2), h
 Staggered form of ethane (C2H6)
Point group D3d - symmetry operations are E, 2C3, 3C2, i, 2S6, 3d
 Eclipsed form of ethane (C2H6)
Point group D3h - symmetry operations are E, 2C3, 3C2, h, 2S3, 3v

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Benzene (C6H6)
Point group D6h symmetry operations are E, 2C6, 2C3, C2, 3C2, 3C2, i, 2S3, 2S6,
h, 3d, 3v total 24

There are also some special point groups for linear molecules:
 HCN and CO2
Point groups Cv, Dh respectively Here, we relabel the irreducible
representations according to the same nomenclature for the molecular term
symbols of linear molecules (see later): g,u, g,u etc.
Also, we find symmetry operations such as C and C2, in addition to some of
the more usual ones such as E, v and h.

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Point Groups
A point group describes the symmetry of a given type of figure.
Each point group has a definite set of symmetry operations, which is the same
for all figures assigned to the group. Thus, D2h can apply to ethylene, or
naphthalene.
The simplest types of group consist only of rotations:
Cn, Dn, T and O
Cn - cyclic group, elements obtained by successive multiplication of the element
Cn, usually n=1-6 for molecules.
Dn - An n-fold axis and n-2-fold axes symmetrically placed in a plane
perpendicular to the principal axis. Dn has all the elements of Cn, which is a
subgroup of Dn. Dn is the group of the propeller:
- biphenyl belongs to D2
- triphenylmethyl radical belongs to D3
- hexaphenylbenzene belongs to D6.
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T is the group of the regular tetrahedron, considering only rotations,
leading to 12 elements.
O is the group of the regular octahedron, considering only rotations. There
are 24 elements here.
The rest of the groups involve reflections, so that the group of the full
octahedron, Oh, has 48 elements.

A fifth type of group of much


current significance is the
icosahedral group, I. Including the
mirror planes, the point group Ih is
the point group of
buckminsterfullerene, C60, or a
soccer ball.
What are the symmetry operations?

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Full Character Table of the Point Group C2v : V- or U-shaped molecules
(water, 1,2- and 1,3-dichlorobenzene, cis-dichloroethylene).

e.g. angle bisector H2O

e.g. H2O out of plane


e.g. plane of H2O mol

http://www.webqc.org/symmetrypointgroup-c2v.html

4 different symmetry operations E, C2, v (xz), v (yz)


4 irreducible representations A1, A2, B1, B2
 A symmetric w.r.t. C2, the highest-order rotational axis.
 x,y,z Cartesian axes belong to different IRs
also applies to one-photon electric dipole transitions
- these correspond to infrared-active vibrations.
 Rx, Ry rotation about the x-axis etc.
 x2, xy etc., - apply to Raman and other two-photon transitions
 The dimensionality of the group is 4. Either the number of IRs including
weighting for the sizes of the matrices (i.e., 1, 4, 9) or the total number of
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symmetry operations, including multiples.
MO1 -20.2 H [A1] MO2 -1.27 H [A1] MO3 -0.62 H [B2]
y

MO4 -0.45 H [A1]

MO5 -0.39 H [B1]


Diagram rotated by
/2 about horizontal
axis

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Matrix multiplication table
Here is a matrix multiplication table for the point group C2v (e.g., water).
This shows the effects of sequential operations. Some are easy to see from
simple diagrams, whereas others are less obvious.

H H
O y

The table is symmetric, which means that all of the operators commute the order in
which operators are applied is irrelevant. This defines an Abelian group.
An important property of a group is that any sequence of operations is
equivalent to a single operation by any member of the group. Thus, the
elements in the multiplication table are all group members.
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Lets summarize the effects of applying the symmetry operations on the
different Cartesian axes of the water molecule:
plane of molecule

The top three lines in the above table are irreducible representations,
whereas their sum, the fourth line is a reducible representation.
Each number in the table represents the trace of a matrix for a particular
symmetry operation. That is, each symmetry operation is a mathematical
operation. The numbers in the top three lines represent 1-D matrices and
those in the bottom row, 3-D matrices.
Each 3-D transformation matrix in the point group C2v can be expressed as
the direct sum of three 1x1 matrices, which is expressed in block diagonal
form.

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Matrices representing operations in the C2v point group

Note that there are no off-diagonal elements in any of the matrices. This tells us
that each matrix can be broken down as a sum of three different 1x1 matrices.
That is, the x, y & z axes have distinct symmetry properties in this point group.
Each matrix is reducible, which means that the representation (x+y+z) is
reducible. The matrices representing
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Symmetry and y andTheory
z individually are all irreducible.
11
When these matrices are multiplied together, the results are the same as when
the operations are performed consecutively. For example, when we perform
C2 and then v (yz) , the matrix representation is:

v(yz) C2 v(xz)

Maple:

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The Point Group of C2h - trans-1,3-Butadiene S- or Z-shaped molecules

H H
H C2 C4
1 C C3 H
H H

http://www.webqc.org/symmetrypointgroup-c2h.html

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The point group D3h and two-
dimensional irreducible
representations
Consider the point group D3h,
which applies to the trigonal
planar molecule BF3.

http://www.webqc.org/symmetrypointgroup-d3h.html

 E and E are two-dimensional IRs, the 2x2 transformation matrices being


irreducible due to the presence of non-zero off-diagonal terms. (See below)
 The C3 operation couples the x and y axes, so that they form a degenerate
pair. (Note the use of parentheses to indicate the degeneracy).
 The dimensionality (order) of the group is 12
 This is a non-Abelian group, where the order of consecutive operations
affects the outcome. (i.e., notSymmetry
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and Group Theory 14
Each symmetry operation can be represented mathematically by an operator:

Matrix Notation for Rotational Operations

New y axis Old y axis

Fixed point P:
Old coords: P (x,y)
New coords: P(x,y)

r New x axis

Rotate axes by
an angle

Old x axis

Rotate axes counterclockwise by , so that the coordinates of the point P change.

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Thus, the rotation operator, expressed as a 22 or 33 matrix, operates on the
vector representing the original x,y (z) coordinates to produce a new vector
containing the new coordinates (x,y(z)). [z coord doesnt change here]

Some rules for


matrix
multiplication

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The matrix in trigonometric functions of is known as the rotation matrix.
Therefore, if our rotation angle in two dimensions corresponded to a C3
operation, for example, then = 2/3 and the rotation matrix in two dimensions
would be:

The TRACE of the matrix (sum of the NW-SE diagonal elements) is the same for
the same type of operator, independently of the choice of coordinate system.
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In 3-D:

Here the trace refers to a basis of three Cartesian vectors (or a set of p-orbitals).
It could be different for some other property (such as molecular vibrations) as
is readily seen from character tables (see below).
Different symmetry operations have distinct matrices, the value of the trace
depending on the context (see supplement):

Note that adding the extra dimension to accommodate the z-axis in effects adds
a 1x1 matrix along the diagonal to the original matrix. The new matrix is
11/27/2016 whereas the component
reducible, Symmetrymatrices
and Groupare irreducible.
Theory 19
The 3x3 matrix below is the sum of a 2x2 for the xy axes and a 1x1 for the z-
axis, having traces -1 and 1, respectively.

This three-fold axis is a key determining factor to the degeneracy of the x and y
axes. Thus, any property of a D3h molecule such as BF3 can be understood in
terms of a pair of equivalent axes (x,y) and a unique axis (z).

Three principal such properties include: molecular orbitals, vibrational modes,


moments of inertia
The same goes for any molecule having at least a 3-fold symmetry axis, such as
NH3, CH3Cl, CH4, C6H6, SF6.

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Reducible Representations, A More General View (see p. 485)
This time, lets consider the molecular orbitals of butadiene what types of
symmetry-adapted combinations are there? First, the answer and then lets see
how group theory arrives at this. This would be clear, for example, from the
symmetries of the different Hckel orbitals.

The allowed linear combinations of the out-of-plane p-orbitals must conform to


the rules of the molecular point group.
Also, we anticipate that the set of four p-orbitals will contribute to a reducible
representation of the point group, the components of which are shown above.
How do we do this?

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Set up transformation matrices for the set of four p-orbitals

p2 p4
p1 p3

Apply the symmetry operations of


C2h point group to the set of four
p-orbitals.

A valid symmetry operation


superimposes one onto another
with either the same or opposite
sign.

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Maple routine doing the same thing

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Theres a quick, and clear way to do arrive at the traces of the transformation matrices
without explicitly writing out the matrices:
p2 p4
p1 p3

We are concerned only with the trace the sum of the diagonal elements.

The diagonal elements are only non-zero if the orbitals stay in place or are,
at most, inverted. Thus:

E all four orbitals remain unchanged Trace = +4

C2 all p-orbitals move - Trace = 0 - nothing remains on the diagonal.

h all p-orbitals invert but stay in place Trace = -4

i all orbitals move Trace = 0 - nothing remains on the diagonal.


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Then compare the characters of the reducible representation against the rest of
the character table:

 Each irreducible representation of a given point group is unique, each one has a
symmetry label, such as Ag, and there is a definite number of them.

 There is an unlimited number of reducible representations of any point group,


commonly labeled , depending only on the property being represented.

Note the mistake in M &S p. 486, where they mislabel the h operation as v.

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We have already given the answer that the set of four molecular orbitals contains
2Aus and 2Bgs.
McQuarrie & Simons book (Eq. 12.22) quotes a formula that can determine the
number of times, a(red,i) an IR, i, appears in a reducible representation, red:

Basically multiply the two representations (i.e., one reducible and one
irreducible), character by character for each one of the symmetry operations R ,
and divide the result by the dimensionality, h, of the point group.
Test Example how many times does Ag appear in the RR for the MOs:
h=4

Also:
Etc.

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This works well for simple
A simple Maple approach involves vector multiplication: point groups such as C2v
and C2h, but needs a slight
modification in other cases

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Using similar procedures, we can show that the set of 6 pz-type molecular orbitals for
benzene corresponds to a reducible representation (MO) within the point group D6h,
which is the sum of the IR's: A2u, E1g, E2u and B2g.

B2g

E2u

E1g

A2u

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This is a top view.
The sign of each MO
changes below the
molecular plane.

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orbitals of benzene labeled according to IRs in the point group D6h. Easily identified since
they all involve only 2pz orbitals on the carbon atoms. Group theory generates a reducible
representation:
11/27/2016 = (A2u + B2g + E1g + ESymmetry
2u). The remaining orbitals are -type. 36 total orbitals 30
and Group Theory
comprise the minimal basis set, accounting for core and valence electrons.
http://www.webqc.org/symmetrypointgroup-d6h.html

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Atomic Motional Degrees of Freedom, and Molecular Vibrations
A molecule containing n atoms requires 3n coordinates of motion to
describe the motion of all the atoms.
Since the molecule is bound together:
3 of these degrees of freedom are reserved for motion of the center
of mass (translation)
Either 2 (linear molecule) or 3 (nonlinear molecule) more are used
to describe rotational motion.
This leaves 3n-5 (linear) or 3n-6 (nonlinear) degrees of freedom to
describe vibrational motion.

Assignment of degrees of motional freedom to symmetry notation allows us to


predict spectroscopic properties and selection rules.

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Trans (z); a1
Rot (x); b2

O O
H H H H

O O
H H H H
Vib symm str; a1 Vib bend; a1

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Reducible Representations
Which motions correspond to which symmetry classifications?
In simple cases, this is straightforward, but for complex molecules we need a
mathematically sound approach.
Again, we set up a reducible representation and then find its components.

Each atom has three motional z


coordinates.

In forming each RR matrix,


we consider not only the y
atomic positions, but also the
x, y and z vectors on each
atom.

See Section 13.10 x

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z

y
z O z

y y
HA HB
We take the x-axis to be out of the molecular plane.

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9x9 Matrix Describing the C2 operation on the x,y,z Atomic Vectors of Water

HA HB O
x

y
HA
z

HB

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y andz Group Theory 36
9x9 Matrix Describing the C2 operation on the x,y,z Atomic Vectors of Water
Instruction:
Exchange positions of
atoms HA and HB, and invert
the x and y vectors of each

Keep O2
atom where
it is , but
invert x and
y vectors

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9x9 Matrix Describing the C2 operation on the x,y,z Atomic Vectors of Water

We are only
concerned with the
trace, which here is -1.

Only atoms that dont


move under the
symmetry operation
contribute to the trace.

Therefore, we can
usually compute the
trace by simple
inspection

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Two of the 9x9 matrices
shown, for the C2 and
v(xz) operators:

Tr(C2) = -1

Tr(v(xz)) = +1

Similarly:

Tr(E) = +9

Tr(v(yz)) = +3
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The traces of the 9x9 matrices for each symmetry operation are entered
as the characters of the reducible representation ((total)) in the C2v
character table.

As before, we can find the component IRs of the RR (total) either manually via the
method of Slide 25 (and M&S Equation 12.23 and Example 12-12), or we could have
Maple do it for us by vector multiplication (Slide 26).

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See p. 526 (Chapter 13)

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Vector Multiplication Approach.

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From this, we find:
(total) = 3A1 + A2 + 2B1 + 3B2 (See page 526)

This reducible representation can be subdivided into translational, rotational


and vibrational components:
(total) = translation + rotation + vibration
We can deduce from the character table that:
translation = (x) + (y) + (z) = A1 + B1 + B2
rotation = A2 + B1 + B2
We deduce by subtraction that:
vibration = 2A1 + B2

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A1 1600 cm-1

A1 3650 cm-1

B2 3750 cm-1

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What determines whether a vibrational or rotational mode is observable as an
absorption band? The following integral must be non-zero.

= final H ' initial d


Well say something more later about this integral (transition dipole moment),
but right now, we can stipulate that the following symmetry based analogue
must be totally symmetric (or contain the totally symmetric representation).
Otherwise, it would generate an odd function, which would integrate to zero:

( )
final H ' initial = symmetric
We can simplify the idea greatly by recognizing that, in an infrared spectrum,
the molecules are usually starting from the zero-point level. This is a symmetric
state, corresponding to the most symmetric representation of the molecular
point group (i.e., the top line of the character table, usually designated A1, Ag or
something similar). In order for the remaining two items to generate a
symmetric result, they must correspond to the same symmetry representation.
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If the operator is an electric dipole operator, which is the case for a 1-photon
transition, then it can be taken to have the same symmetry species as one of the
Cartesian axes.
Suppose we have a B2 vibrational mode in the water molecule. This will
correspond to the condition: final = B2. The above symmetry relationship requires
that () = B2, since B2 x B2 x A1 = A1. This can be checked by multiplying the
rows of the different representations, operation by operation.
This result shows that the transition from the zero-point energy to the B2
vibrational mode can be facilitated by a y-polarized photon. Normally, we dont
care which polarization is involved, as long as there is a fit.
Bottom line. A vibrational mode (or a rotation) will appear in the infrared
(or microwave) spectrum if the representation corresponding to that mode also
matches one of the three Cartesian axes. Its as simple as that.

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Infrared and Raman Selection Rules for Polyatomic Molecules
We assume a totally symmetric ground state, which is the case for the
large majority of molecules.
In the infrared spectrum, those vibrational modes having the same
symmetry as one of the Cartesian axes will have nonzero transition moment
matrix elements. Therefore, the vibrations should be infrared active.

Infrared Spectroscopy (or Microwave)


Light is absorbed (or emitted) between two levels.

Vib (IR) or Rot (-wave) level


Absorption Emission

Ground state

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Raman Scattering
Photon (commonly but not necessarily derived from a laser) is
inelastically scattered from a molecule.

Virtual level
In Raman spectroscopy, since we
have a two-photon process, the
transformation is represented by
the quadratic products of x, y Raman-scattered
Laser photon
and z. Such modes would be photon
Raman active.

Vib or rot level


Different combinations of
incoming and scattered photon
Ground state
polarizations are appropriate for
different vibrational modes.

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Spectrometer

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Let's take, for example, the D3h character table, which represents BF3:

+1
} RRs for trans, rot and
vib degrees of freedom

Because of the 3-fold axis, there are some 2-D irreducible representations (IRs).

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Ethylene (C2H4) Point Group D2h (Note: All IRs are 1-D)

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Group theoretical analysis yields:

Mutual Exclusion Rule for centrosymmetric molecules: Vibrational modes can be IR active or
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Raman active, or neither. However, no mode can be both Raman and IR active.
Ethylene does not have a pure-rotation (microwave) spectrum.
The rotations all have g symmetry and do not correspond to the Cartesian vectors, which
are all u. It needs a permanent dipole moment to have a microwave spectrum.

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BF3 also does not have a pure rotational spectrum. Although they are not
centrosymmetric, D3h molecules dont have dipole moments. In group theory, we
examine whether any of the Rx, Ry or Rz have the same symmetry as x, y, z.
Evidently not!

+1

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C3v molecules NH3, CH3Cl, CHCl3

For spectroscopic activity, we look to see whether Rx


etc. corresponds to the same symmetry classification as
x, y or z.

Rotation about the z-axis is spinning about the


molecular axis. There is no fluctuating dipole. No
microwave transition.

Rotation about either x or y is end-over-end rotation


and is observed in the microwave spectrum.

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http://www.webqc.org/symmetrypointgroup-d6h.html

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Benzene vibrational modes. There are 30 modes with 20 distinct frequencies.

Source NIST Webbook:


webbook.nist,gov

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Most of the vibrational features are the same in the gas and liquid phases, especially where
intermolecular forces are weak. Gas-phase IR transitions tend to be broadened by rotational
substructure.

Gas

Liquid

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